Process of making ethereal salts of formic acid.



have found that such mixed anhydrides can.

NITED STATES PATENT OFFICE,

AUGUSTE BEHAL, OF PARIS, FTQANCE.

PROCESS O F MAKING ETHEREAL SALTS OF F- ORMI-CACID.

SPECIFICATION forming part of Letters Patent No. 648,580, dated May 1, 1900. Application filed November 29, 1899. Serial No. 73 8,716. (Specimen) useful Improvementsin Processes of Making Ethereal Salts of Formic Acid, which are fully described in the following specification.

Hitherto no mixed anhydride of formic with other organic acids has been produced. I

be readily obtained by causing formic acid free from water to react on anhydrides of organic acids at moderate temperatures. The

reaction is rapid, and the. mixed anhydrides thus obtained may be characterized by the fact that they are decomposed in the cold by tertiary bases, (quinolin, pyridin, dimethlanilin,) disengaging plentifully carbon monoxid. 1 r

products thus obtainedare mere-mixtures. Bymy process the reaction isbetween an-' hydrous formic acid and the anhydrides of organic acids, and the products are undoubtedly compounds'true mixed anhydrides. The reactions of theselmixed anhydrides (R000. 1

CH0) on. alcohols (R .OH) and on ammonia or substituted ammonias (NH R NHR R maybe expressed by the following equations:

These mixed anhydrides act upon acyclic or Autenrieth (Bcnd. D. Chem. Gesgvollfio,

mic-acetic anhydride is prepared by mixing equal molecular proportions of formic acid free from water and acetic anhydride, care being taken that the temperature does not exceed 50 centigrade. The mixed anhydride at once results. i It is scarcely soluble in pe- By agitating the product of troleum ether. 7 the reaction with petroleum ethera considerable portion of the acetic acid is removed;

The portion not dissolved in thepetroleum ether constitutes the raw mixed formic-acetic anhydride, which is purified by fractional and repeated distillationin cacao. It is a body pheric pressure at 105 to 118 centigrade,

with partial decom'positionand evolution of carbon monoxid. It distils at about 29 centigrade under eighteen millimeters pressure. p.

I It is decomposed in the cold by tertiary'bases,

anhydrous sodium acetate, and the like, with abundant evolution of carbon monoxid.

ML QZGd formic propion'ic anhydride.-This uct shows all the reactions of themixed formic propionic anhydride. In cacao it distils Without change, but whendistilled at the or- -di'nary pressure it decomposes, carbon monoxid being evolved. Like formicacetic an- 1 hydride it decomposes 1n contact with quincline, yielding carbon monoxid. It reacts with alcohols in the cold, giving formic others. For example, with hexylic alcohol it yields hexyl formate.

llf'ixed for-mic z'so-naleric anhydride.-This is prepared in a similar manner. The evolution of heat is less marked than in the preceding cases. It reacts with alcohols, yielding formates. Thus with caprylic alcohol it yields capryl formate.

Mixedformz'c iso-butyric anhydride.-This is prepared .like the preceding and reacts in a similar manner.

For-mate of capryL- To one molecular proportion of caprylic alcohol is added while cooling somewhat more than one molecular proportion of mixed anhydride, such as formic acetic anhydride. The reaction is very rapid. It is found unnecessary to isolate the mixed y anhydri de iniaflpuitestate, asthefree acetic acid doesnot interfere with the reaction. On. distilling the firstportions are acetic acid and,

v the more-highly rectified portions are formate of caprylt It isa liquid having an aromatic ordinarypres'sui'e, without'sensib'le' alte1a'-' tion. -ItsAenSitY-tat 0 centigrade is 0884,

- The samefformatexof caprylmayalso' bB'iptB-I i0 pared by using formic iso-valeric anhydride'v l I instead of formio-aceticanhydride.

odor, boiling at 185 to ISiG -centignadeunden Jfet'her; )It crystallizes very easilyat zeroin The formatespt gethy ethy1,,"prop yl-,-iso-1 Foimaifiltd. iit-bn -itoiecuiar proportion ateofhex lib as been lotai ned- *niIe -piioeejss both 'ib'yguse offo mic acetic 1 ute'ether, of which a considerable-quantity has to be taken because forinamid is only slightly soluble: in ether; On cooling, when thesolution smells'strongly'of ammonia-gas,

, 7 the ether is separated by decanting from the crystalsrthat'ai'e formed: The ether distilled leaves the tforinamid. Contrary to received data the foiniamid is very slightly soluble in- 75 long characteristic needles fusible at about M'tcentigfade. Itb'oils under a pressure of thirtyr't we :1} millimeters Without decomposi- The reaction pr d uct isi-washed ydiochlo I,

' vesgthei tofnianiw thylanilin there fiSI o boitneohinientho geraniol lin'alool'; ronellojlg} terpineolg dzc-g; whi'clii have' known Y sity of L067 at"27- eentigrade; The-reaction 5 5 also takesplaoe with sesq'ui-terrpenic aleoholsk With caryophyllenicalcohol is obtained the formateof caryophylle'nyl, whosedensity at l 0 centigl ade is l.O266; boilingpoin't 167f"toi 170 centigrade, under twenty-seven lmilli- '6o meterspressure- -With santalol is obtair'ied the formate of santalyl, hich'boil s at175 to 178 centigi ade under twenty-seven millimeters pressure and has density of 1.0180at T 0 ce'ntigrade. I 65 FoTmdm'id.-'Amm0nia;gas is introduced t l ti n of iIIllXQliflllhYdlldG in abso- I I I I I I I fllowszjOne-molecu1ar p'i o'po itionof fonnie acid characteristics With" anhydfous -terpingi's 1 obtain'edterpin difoi'rna te, which boilsat 176 to {177 centigrade under. foity'milliinete 'sfi pressure and is a syrupy liquid having a den-: I

* absolute anhydrous ether afndthe' inixedl'a'ne rying the same into practical efiect-,Iclaim is i'ad(led; to one moleeulaig proportion ofi Vadride. Next: phenyl-hydifa'zin is; dissolved in hydi'ideis added-thereto little by little, when tormylph'enylhydrazin is -p1 ecipitated ;Z Itiis i Having thus described "the nature of this invention and the bestmeans I know of "car.-

I I 30 1;, The processhereindescr-i-bed for the man- 'i1fac ture of mined anhydridesotfo jlnicacid with another organic acid and fractionally distilling the product.

In witness whereof I have hereunto signed 7 my name, this 17th day of November, 1899, in the presence of two subscribing witnesses. 15

AUGUSTE BEHAL.

Witnesses:

J ULES ARMENGAUD, Jeune, I. ALLISON BOWEN. 

